CN101402790A - Sulfonation phenylphosphonic acid zirconium doping proton exchanging film and method of producing the same - Google Patents
Sulfonation phenylphosphonic acid zirconium doping proton exchanging film and method of producing the same Download PDFInfo
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Abstract
The invention relates to a proton exchange membrane adulterated with sulfonation zirconium phenylphosphonate which is characterized in that: the film-making material thereof consists of a sulfonation high molecular material and sulfonation zirconium phenylphosphonate; wherein, the sulfonation degree choice of the sulfonation high molecular material is 20 percent to 85 percent which accounts for 60 percent to 95 percent of the mass percent of the film-making material; and the sulfonation degree choice of the sulfonation zirconium phenylphosphonate is 30 percent to 90 percent which accounts for 5 percent to 40 percent of the mass percent of the film-making material. Besides, a porous supporting material can be added to the film so as to improve the strength of the film and reduce the deformability thereof. The film-making material fills the holes of the porous supporting material and forms a layer of thin film on the outer surface of the porous supporting material. The proton exchange membrane is applicable to intermediate temperature direct methanol fuel cells so as to improve the application temperature of the proton exchange membrane and the property of the fuel cells.
Description
Technical field
The present invention relates to proton exchange membrane of a kind of sulfonation phenylphosphonic acid zirconium doping and preparation method thereof.
Background technology
Proton exchange membrane is the core component of proton exchange fuel cell (PEMFC), and it serves a dual purpose in fuel cell.On the one hand, play protolysis as ionogen, on the other hand, as the dipolar material of dividing plate barrier material.At present, Proton Exchange Membrane Fuel Cells mainly adopts the perfluoro sulfonic acid membrane Nafion film of du pont company.This class film properties excellence, but after temperature was higher than 90 ℃, because dehydration, the specific conductivity of film can significantly descend.In addition,, cause the cathode performance decay, can reduce the serviceability of direct methanol fuel cell (DMFC) greatly because the Nafion film to the transmitance height of methyl alcohol, makes negative electrode produce mixed potential.
At present, the key technical problem of DMFC exploitation is the saturating pure problem of the low and film of activity of such catalysts.Solving above two problem effective ways is the working temperatures that improve fuel cell.Can improve activity of such catalysts because improve the working temperature of battery.Because the lifting of speed of reaction, reactant is reacted away on electrode at once, can reduce the chance that reactant sees through film greatly.Moreover, because the raising of working temperature makes toxicant desorption on the catalyzer, reaction accelerate, can not cause the poisoning of catalyzer, so the raising of the battery operated temperature of DMFC can improve the performance of battery greatly.For PEMFC, the raising of working temperature can reduce the requirement of battery to fuel purity, promotes its commercialization.
At present, if think that in the world the working temperature of PEMFC, DMFC can reach middle temperature (120 ℃～180 ℃) performance of battery is significantly improved.Under this temperature, materials such as the catalyzer of battery, bipolar plates, sealing material all can continue use, and just the Nafion mould material that uses at present can not use.So but the proton exchange membrane material that the novel medium temperature condition of development research uses down is its key problem in technology.Development research as middle temperature proton exchange film material concentrates on the phosphate-doped polybenzimidazole (PBI) [Si lva, J.Power Sources, 145 (2005) 485-494] of employing, because the PBI cost is higher, so its commercialization is restricted.Also have and mix 1,2, the specific conductivity of Nafion115 film when the report of 4-tri carboxyl butane-2-phosphonic acids zirconium and sulfonated polyether-ether-ketone CN1713426A (2005) such as [] Wang Yuxin preparation heatproof proton exchange membrane, its temperature specific conductivity in the time of 160 ℃ can reach 0.09S/cm and be higher than 90 ℃.
The polyaryletherketone compounds is the good functional materials of a class, as polyether-ether-ketone (PEEK), can obtain sulfonated polyether-ether-ketone (SPEEK) with vitriol oil Direct Sulfonation.Its thermogravimetric analysis demonstration polymkeric substance below 400 ℃ is not degraded, and 240 ℃ of later sulfonic groups just decompose, and have thermostability preferably.Sulfonation degree is 65% PEEK, and the sulfonic group concentration among its loading capacity and the Nafion-117 is suitable, has higher proton conductivity [Jones D J, J.Membr.Sci., 2001,185:41].But SPEEK also has the shortcoming of himself, and its proton conductivity is bigger to the dependency of water than Nafion-117, and could be suitable with Nafion-117 electroconductibility under high water content, and higher swelling capacity is arranged.
In order to improve the water content of film, strengthen its alcohol-rejecting ability, reduce its swelling capacity, people such as V.S.Silva [J.PowerSources, 2005,140 (1): 34-40] have prepared SPEEK/ZrO
2The organic and inorganic composite membrane though this class film has good alcohol-rejecting ability, is compared with pure film, and proton-conducting descends, and also has the scholar to mix with heteropolyacid and prepares composite membrane, but because it is higher water-soluble, can not be used under high temperature, the high humidity environment.
Assorted naphthalene biphenyl class organic polymer also is the functional materials of a class superior performance, is characterized in heat-resisting, solvable, wear-resisting, chemistry and good mechanical stability, behind the sulfonation modifying, has higher proton conductivity.As assorted naphthalene biphenyl polyether sulfone (PPES), assorted naphthalene biphenyl polyether sulfone ketone (PPESK), assorted naphthalene biphenyl polyether ketone (PPEK), can in oleum, sulfonation make corresponding sulfonated products SPPES, SPPESK, SPPEK, not only have good proton conductivity with its proton exchange membrane of making, also have thermostability and physical strength preferably.[J.Membr.Sci., 2003,227 (1-2): 39-50] such as Gao Yan have investigated the performance of SPPESK film, have reported water-intake rate, swelling capacity and the specific conductivity of film.[J.Membr.Sci., 2006,281 (1-2): 121-129] such as Gu Shuang have also prepared the assorted naphthalene biphenyl polyether sulfone ketone film of sulfonation with mixing acid as sulphonating agent, have investigated its alcohol-rejecting ability, and 80 ℃ of sulfonation degree are that 81%, 91% film electric conductivity is respectively 1.3 * 10
-2S/cm and 3.0 * 10
-2S/cm.In order to reduce the swelling capacity of SPPESK film, improve its alcohol-rejecting ability, [J.PowerSources, 2006,155 (2): 111-117] such as Su Y.H. have prepared SPPEK/SiO
2Composite membrane, nanometer SiO
2Evengranular being distributed on the polymeric matrix improved the swelling behavior, improved thermostability and mechanical property, and methanol crossover obtains improvement to a certain degree, but proton conductivity has necessarily and reduces.
Phosphoric acid hydrogen zirconium (ZrP) and derivative thereof be because himself advantage, as higher loading capacity, thermostability, water insoluble, acid etc., makes it become good high-temperature proton-conductor.People [J.ColloidInterface Sci., 316 (2007) 612-621] such as Bijay P.Tripathi have prepared the SPEEK/ZrP composite membrane with electrochemical migration and in-situ precipitate method.At room temperature, the proton conductivity of composite membrane is lower than the SPEEK film, but has improved proton conductivity at high temperature.
With phosphenylic acid (C
6H
5PO
3H
2) Zr in the precipitation solution
4+Ion can get phosphenylic acid zirconium (ZrPP).This compounds has the similar laminate structure of α-ZrP, and water insoluble and organic solvent, has acidity and hydrophobicity, and thermostability is very high.Sulfonation benzene sour zirconium (the Zirconium Sulphophenylphonate that sees, ZrSPP) be in laminate structure, to introduce the Phenylsulfonic acid base, has good proton exchange, proton conductivity has improved three orders of magnitude than ZrP, even under the situation of lack of water, the ionogen in middle layer can make proton jump, and is an acidic catalyst or the ion-exchange material of heterogeneous catalytic reaction.
Summary of the invention
Technical problem to be solved by this invention provides proton exchange membrane of a kind of sulfonation phenylphosphonic acid zirconium doping and preparation method thereof, and prepared proton exchange membrane is used for fuel cell, can use down in middle temperature (120 ℃～180 ℃).
The proton exchange membrane of sulfonation phenylphosphonic acid zirconium doping of the present invention, it is characterized in that its material of preparing is made up of sulfonated polymer material and sulfonation phenylphosphonic acid zirconium, wherein the sulfonation degree of sulfonated polymer material selects 20%～85%, the mass percent that accounts for material of preparing is 60%～95%, the sulfonation degree of sulfonation phenylphosphonic acid zirconium selects 30%～90%, and the mass percent that accounts for material of preparing is 5%～40%.
The proton exchange membrane that the present invention obtains belongs to the inorganic-organic hybridization film.Wherein:
The sulfonated polymer material can be selected Sulfonated heteronaphthalene biphenyl poly-ether-ketone (SPPEK), the assorted naphthalene biphenyl polyether sulfone (SPPES) of sulfonation, sulfonated polyether-ether-ketone (SPEEK), sulfonated polyether sulfone (SPES) or the assorted naphthalene biphenyl polyether sulfone ketone (SPPESK) of sulfonation etc. for use.
The present invention can also add porous support materials in film, improve film strength, reduces deformability.The hole of the filling porous propping material of material of preparing (being made up of sulfonated polymer material and sulfonation phenylphosphonic acid zirconium) also forms thin film at the outside surface of porous support materials, the proton exchange film thickness of preparation is 30～200 microns, the thickness of porous support materials is 10～70 microns, voidage is 30%～90%, the aperture is 0.01～0.2mm, and porous support materials accounts for 1%～40% of material of preparing total mass.
Porous support materials can be porous polymer materials, porous cloth, molecular sieve, mesoporous metal plate, porous ceramics or porous asbestos plate.Preferably polytetrafluoroethylene net, porous ceramics (thin slice) or expanded metal.
The method of the proton exchange membrane of preparation sulfonation phenylphosphonic acid zirconium doping, be that the sulfonated polymer material is dissolved in the certain amount of organic solvent, adding sulfonation phenylphosphonic acid zirconium again mixes, filtration, sonic oscillation are removed bubble, be made into preparation liquid, casting film, the mass concentration of sulfonated polymer material and sulfonation phosphenylic acid salt mixture is 2wt%～40wt% in the preparation liquid.
Described organic solvent is generally dimethyl formamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) etc.
When containing porous support materials, porous support materials is dipped in the proton exchange membrane that forms the band porous support materials in the preparation liquid, material of preparing should fill up the hole of porous support materials, also is wrapped in one deck material of preparing in the outside of propping material simultaneously, forms smooth, fine and close mould material.
Below than describing the preparation method in greater detail.
1, macromolecular material sulfonation
The preparation of the assorted naphthalene biphenyl polyether sulfone (SPPES) of sulfonation
Electric mixer is being housed, reflux condensing tube, add 3g PPES in the there-necked flask of dropping funnel, under heating in water bath, stir and drip the mixing solutions of vitriol oil and oleum (its volume ratio is 1: 1～1: 2) to it, drip in 10～30min, under 60 ℃～80 ℃, reflux, stir 3～5h, reaction is finished, and the supernatant liquor in the there-necked flask is inclined to, bottom brown thick liquid poured in the mixture of ice and water reel off raw silk from cocoons, obtain white filament, wash with water, put into vacuum drying oven inner drying 24h to neutral (PH is about 7).Take out and pulverize, be washed till PH and be about 7, suction filtration is put into vacuum drying oven inner drying 24h with filter cake, pulverizes, and obtains white powder.Measure sulfonation degree.
2, ZrSPP preparation
2.1 the preparation of phenyl-phosphonic acid
Electric mixer is being housed, and reflux condensing tube adds the 26.6mL phosphorus trichloride in the there-necked flask of dropping funnel, the 6.5mL dry benzene, and the 11g aluminum trichloride (anhydrous) stirs, and slowly is heated to the benzene boiling.Reflux 8h.Stop heating, drip the 18mL phosphorus oxychloride while hot, 0.5h drips.Add the 40mL sherwood oil again, backflow 0.5h.Cooling gets yellow thick liquid.Must hard solid with yellow thick liquid with petroleum ether.Steam sherwood oil, get weak yellow liquid, yellow crystals is arranged, leave standstill 6h, get faint yellow paste, agitation and filtration gets yellow powder behind the adding ethanol.
2.2 the preparation of phenylphosphonic acid zirconium
Get 6.46g ZrOCl
2.8H
2O puts into polytetrafluoroethylplastic plastic bottle 1, adds the 20mL deionized water, makes its dissolving, adds 14mL HF.Get the acid of seeing of 6.48g benzene and put into Plastic Bottle 2, add the 180mL deionized water and make its dissolving, stir down the material in the Plastic Bottle 1 is added in the Plastic Bottle 2.60 ℃ of stirring reaction 72h.Adularescent crystallization generation, suction filtration in the solution, filter cake is washed till in the filtrate till the no chlorion with deionized water.It is dry to put into loft drier.Get white powder.
2.3 the preparation of sulfonation phenylphosphonic acid zirconium
Electric mixer is being housed, reflux condensing tube, add the 3g phenylphosphonic acid zirconium in the there-necked flask of dropping funnel, with the ice-water bath cooling down, mixing liquid to wherein dripping the vitriol oil and oleum (its volume percent is 1: 1～1: 2) stirs, and puts into heating in water bath, under 60 ℃, stir, refluxed 2 hours.After sulfonation finishes, mixture is put cold, stir, pour in the mixture of ice and water, to wherein adding deionized water, after the clarification, supernatant liquid is carefully shifted out, and repeatable operation three times is then with the mixture suction filtration in the beaker, and with deionized water will be wherein foreign ion and remaining sulfuric acid flush away, it is closely neutral to be washed till filtrate.With filtration cakes torrefaction, obtain white powder.
3, the preparation of SPPES/ZrSPP composite membrane
2.00g SPPES (DS=81%) is dissolved in a certain amount of N,N-dimethylacetamide, and magnetic agitation 12h fully dissolves.Vacuum filtration is removed insolubles and impurity thereof, adds a certain amount of ZrSPP, is made into the preparation liquid of about 10wt%.Behind the magnetic agitation 6h thorough mixing, ultra-sonic oscillation 1h to remove bubble, transfers to casting film-forming on the sheet glass of the cleaning of horizontal positioned then.60 ℃ of dry 24h, dry 4h under 100 ℃ then.
4, the preparation of the SPPES/ZrSPP composite membrane of porous material support
To adopt porous PTFE fabric is that example prepares the enhanced polymeric film material
Get the thick PTFE film of treated 0.1～0.05mm, voidage 50%～80%, the mass concentration that immerses sulfonated polymer material and sulfonation phosphenylic acid salt mixture is in the preparation liquid of 2wt%～40wt%, soak 1～4h, taking-up is tiled on the clean sheet glass at 60 ℃ of following vacuum-drying 4h, and 130 ℃ of dry 8h are standby.
By test shows, the mechanical property of the mould material of porous PTFE fabric-supported, thermostability, solvent resistance are good, meet the standard that the battery membranes material that acts as a fuel uses.Observe by SEM, mould material belongs to smooth, fine and close film, and resolving power is not observed micropore under from the macroscopic view to 20nm, and its section SEM shows that mould material does not have through hole, so this mould material is airtight.XRD analysis shows not have crystal habit in the mould material, shows that such mould material is not crisp, can not cause local gas leakage in the use.
The film-forming method of other preparation liquid is the same, adopts other porous support materials material preparation reinforcing membrane material methods the same.
5, the aftertreatment of film
Taking off in the good film immersion deionized water of drying, then at 1M H
2SO
4The middle 24h that soaks is with residual H in the flushing membrane in the deionized water
2SO
4, be immersed in the deionized water stand-by.
Advantage of the present invention:
The proton exchange membrane of the fuel cell that temperature (120 ℃～180 ℃) is used in of the present invention is to be raw material with SPPES, and it has better thermostability and mechanical property, and can control its proton conductivity and swelling capacity thereof by the difference of sulfonation degree.The ZrSPP that uses among the present invention (or ZrSPP and porous support materials) is water insoluble, and has thermostability preferably, has guaranteed that composite membrane can not cause film properties to descend under high temperature, high humidity environment because mould material is water-soluble.And ZrSPP also has higher proton conductivity, not only increased the mechanical property and the resistance to elevated temperatures of film, can also improve the proton conductivity of film.The better heat stability of this composite membrane, operating temperature range is greater than the Nafion film.Proton conductivity at low temperatures is suitable with the Nafion117 film, and saturating pure coefficient is wanted little two orders of magnitude.When being higher than 120 ℃, has higher proton conductivity.Because the conductivity of film under middle temperature that utilize the present invention to prepare is superior, thus it be well suited for being applied in the warm direct methanol fuel cell, to improve the working temperature of fuel cell, improve fuel cell performance.And much lower with the film cost of this kind method preparation than the Nafion film, help applying of DMFC.
Description of drawings
Fig. 1 is that level is to the conductivity measuring apparatus synoptic diagram;
Among Fig. 1: 1 electrode, 2 proton films, 3 leads, 4 tetrafluoroethylene supports
FRA is the electrochemical impedance test macro
Embodiment
[embodiment 1]: the preparation of the assorted naphthalene biphenyl polyether sulfone (SPPES) of sulfonation
Electric mixer is being housed, and reflux condensing tube adds 3g PPES in the there-necked flask of dropping funnel, use heating in water bath, stir and, drip in 10～30min to its mixing solutions that drips the vitriol oil and oleum, under 60 ℃～80 ℃, reflux, stir 3～5h, reaction is finished, and the supernatant liquor in the there-necked flask is inclined to, bottom brown thick liquid poured in the mixture of ice and water reel off raw silk from cocoons, obtain white filament, wash with water, put into vacuum drying oven inner drying 24h to neutral (PH is about 7).Take out and pulverize, be washed to PH and be about 7, suction filtration is put into vacuum drying oven inner drying 24h with filter cake, pulverizes, and obtains white powder.Measure sulfonation degree (DS).
[embodiment 2]: Sulfonated heteronaphthalene biphenyl poly-ether-ketone (SPPEK), the preparation of the assorted naphthalene biphenyl polyether sulfone ketone (SPPESK) of sulfonation is with embodiment 1, and just raw material being mixed, naphthalene biphenyl polyether sulfone (PPES) changes assorted naphthalene biphenyl polyether ketone (PPEK) respectively into and assorted naphthalene biphenyl polyether sulfone ketone (PPESK) gets final product.
[embodiment 3]: the preparation of sulfonated polyether-ether-ketone (SPEEK) and sulfonated polyether sulfone (SPES) is with embodiment 1, just the assorted naphthalene biphenyl polyether sulfone (PPES) of raw material is changed into polyether-ether-ketone (PEEK) and polyethersulfone (PES) respectively, sulfonated reagent is changed into the vitriol oil get final product.
The sulfonation of other material is with embodiment 1.
[embodiment 4]: the preparation of phenyl-phosphonic acid
Electric mixer is being housed, and reflux condensing tube adds the 26.6mL phosphorus trichloride in the there-necked flask of dropping funnel, the 6.5mL dry benzene, and the 11g aluminum trichloride (anhydrous) stirs, and slowly is heated to the benzene boiling.Reflux 8h.Stop heating, drip the 18mL phosphorus oxychloride while hot, 0.5h drips.Add the 40mL sherwood oil again, backflow 0.5h.Cooling gets yellow thick liquid.Must hard solid with yellow thick liquid with petroleum ether.Steam sherwood oil, get weak yellow liquid, yellow crystals is arranged, leave standstill 6h, get faint yellow paste, agitation and filtration gets yellow powder behind the adding ethanol.
[embodiment 5]: the preparation of phenylphosphonic acid zirconium
Get 6.46g ZrOCl
2.8H
2O puts into polytetrafluoroethylplastic plastic bottle 1, adds the 20mL deionized water, makes its dissolving, adds 14mL HF.Get the acid of seeing of 6.48g benzene and put into Plastic Bottle 2, add the 180mL deionized water and make its dissolving, stir down and add in 21.60 ℃ of stirring reaction 72h.Adularescent crystallization generation, suction filtration in the solution, filter cake is washed till in the filtrate till the no chlorion with deionized water.It is dry to put into loft drier.Get white powder.
[embodiment 6]: the preparation of sulfonation phenylphosphonic acid zirconium
Electric mixer is being housed, and reflux condensing tube adds the 3g phenylphosphonic acid zirconium in the there-necked flask of dropping funnel, to the mixing liquid that wherein drips the vitriol oil and oleum, stir with the ice-water bath cooling down,, put into heating in water bath, under 60 ℃, stirring, backflow 2h.After sulfonation finishes, mixture is put cold, stir, pour in the mixture of ice and water, to wherein adding deionized water, after the clarification, supernatant liquid is carefully shifted out, and repeatable operation three times is then with the mixture suction filtration in the beaker, and with deionized water will be wherein foreign ion and remaining sulfuric acid flush away, it is closely neutral to be washed till filtrate.With filtration cakes torrefaction, obtain white powder.
[embodiment 7]: the preparation of SPPES/ZrSPP composite membrane
Get 2.00g SPPES (DS=81%) and be dissolved in a certain amount of N,N-dimethylacetamide, magnetic agitation 12h fully dissolves.Suction filtration is removed impurity then, adds the 0.2gZrSPP powder, behind the magnetic agitation 6h, puts into ultrasonic wave pond sonic oscillation 30min, and magnetic agitation 30min forms uniform 10% preparation liquid again.Preparation liquid is poured on the homemade glass lamina membranacea, put into loft drier, dry 24h under 60 ℃, dry 4h under 100 ℃ then.After naturally cooling to room temperature, immerse in the deionized water film is taken off.Immerse the H of 1M
2SO
4, soak 24h, rinse well with deionized water, immerse in the deionized water standby.The ZrSPP content of gained film is 10%, and thickness is 0.08mm.The proton conductivity of this film under 110 ℃ is 0.07S/cm, 130 ℃ of specific conductivity 0.08S/cm, and the methanol crossover coefficient of 160 ℃ specific conductivity 0.10S/cm.30 ℃ following this film is 4.3 * 10
-8Cm
2/ s is than low two orders of magnitude of Nafion.
[embodiment 8]: the film-forming method of the sulfonation phenylphosphonic acid zirconium of other sulfonated polymer material, other sulfonation degree, other proportioning and other sulfonation degree is with embodiment 9.The performance test data of different films is as shown in table 1.
[embodiment 9]: the polymeric film material that adopts porous PTFE fabric-supported
[method one] gets the thick PTFE film of treated 0.1～0.05mm, voidage 50%～80%, the mass concentration that immerses sulfonated polymer material and sulfonation phosphenylic acid salt mixture is in the preparation liquid of 2wt%～40wt%, soak 1～4h, taking-up is tiled on the clean sheet glass at 60 ℃ of following vacuum-drying 4h, and 130 ℃ of dry 8h are standby.
[method two] is fixed on the PTFE fabric-supported material two ends in hole on the film balance, regulates the membrane speed of film balance in the PTFE fabric is immersed in above-mentioned (the embodiment 9 methods one) preparation liquid, and slowly oven dry makes required mould material.
By test shows, the mechanical property of the mould material of porous PTFE fabric-supported, thermostability, solvent resistance are good, meet the standard that the battery membranes material that acts as a fuel uses.Observe by SEM, mould material belongs to smooth, fine and close film, and resolving power is not observed micropore under from the macroscopic view to 20nm, and its section SEM shows that mould material does not have through hole, so this mould material is airtight.XRD analysis shows not have crystal habit in the mould material, shows that such mould material is not crisp, can not cause local gas leakage in the use.
[embodiment 10]: the preparation method of film material that adopts other porous material support is with embodiment 9.
[embodiment 11]: the mensuration of the middle temperature specific conductivity of mould material
The determinator of mould material specific conductivity as shown in Figure 1.Its testing method is a known method.It is as a result shown in the table 1.
[embodiment 12]: the mensuration of the methyl alcohol spread coefficient of mould material
The mensuration of the methyl alcohol spread coefficient of mould material adopts known method to measure, and it is as a result shown in the table 1.
Claims (8)
1, a kind of proton exchange membrane of sulfonation phenylphosphonic acid zirconium doping, it is characterized in that its material of preparing is made up of sulfonated polymer material and sulfonation phenylphosphonic acid zirconium, wherein the sulfonation degree of sulfonated polymer material selects 20%～85%, the mass percent that accounts for material of preparing is 60%～95%, the sulfonation degree of sulfonation phenylphosphonic acid zirconium selects 30%～90%, and the mass percent that accounts for material of preparing is 5%～40%.
2, proton exchange membrane according to claim 1 is characterized in that described sulfonated polymer material adopts Sulfonated heteronaphthalene biphenyl poly-ether-ketone, the assorted naphthalene biphenyl polyether sulfone of sulfonation, sulfonated polyether-ether-ketone, sulfonated polyether sulfone or the assorted naphthalene biphenyl polyether sulfone ketone of sulfonation.
3, proton exchange membrane according to claim 1, it is characterized in that comprising porous support materials, the hole of the filling porous propping material of material of preparing also forms thin film at the outside surface of porous support materials, the thickness of the proton exchange membrane of preparation is 30～200 microns, the thickness of porous support materials is 10～70 microns, voidage is 30%～90%, and the aperture is 0.01～0.2mm, and porous support materials accounts for 1%～40% of material of preparing total mass.
4, proton exchange membrane according to claim 3 is characterized in that described porous support materials is porous polymer materials, porous cloth, molecular sieve, mesoporous metal plate, porous ceramics or porous asbestos plate.
5, proton exchange membrane according to claim 4 is characterized in that described porous support materials is tetrafluoroethylene net, porous ceramics or expanded metal.
6, a kind of method for preparing the proton exchange membrane of the described sulfonation phenylphosphonic acid zirconium doping of claim 1, it is characterized in that described sulfonated polymer material is dissolved in the certain amount of organic solvent, adding sulfonation phenylphosphonic acid zirconium again mixes, filtration, sonic oscillation are removed bubble, be made into preparation liquid, casting film, the mass concentration of sulfonated polymer material and sulfonation phosphenylic acid zirconium mixture is 2wt%～40wt% in the preparation liquid.
7, preparation method according to claim 6 is characterized in that described organic solvent adopts dimethyl formamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
8, preparation method according to claim 6, it is characterized in that porous support materials is dipped in the proton exchange membrane that forms the band porous support materials in the preparation liquid, the thickness of described porous support materials is 10～70 microns, voidage is 30%～90%, the aperture is 0.01～0.2mm, and porous support materials accounts for 1%～40% of material of preparing total mass.
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| CN103956506A (en) * | 2014-05-22 | 2014-07-30 | 胡国良 | Preparation method of compound proton exchange membrane for fuel cell |
| CN104549379A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN104993086A (en) * | 2015-05-29 | 2015-10-21 | 深圳市恒力凯科技有限公司 | Lithium polymer battery |
| CN105390721A (en) * | 2015-12-28 | 2016-03-09 | 湖北工程学院 | Method for preparing boron phosphate coated carbon nanotube composite proton exchange membrane |
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2008
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Cited By (6)
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| CN104549379A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN104549379B (en) * | 2013-10-18 | 2017-01-18 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN103956506A (en) * | 2014-05-22 | 2014-07-30 | 胡国良 | Preparation method of compound proton exchange membrane for fuel cell |
| CN104993086A (en) * | 2015-05-29 | 2015-10-21 | 深圳市恒力凯科技有限公司 | Lithium polymer battery |
| CN104993086B (en) * | 2015-05-29 | 2017-09-29 | 深圳市恒力凯科技有限公司 | A kind of lithium polymer battery |
| CN105390721A (en) * | 2015-12-28 | 2016-03-09 | 湖北工程学院 | Method for preparing boron phosphate coated carbon nanotube composite proton exchange membrane |
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| CN101402790B (en) | 2010-12-22 |
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